SiO2@BiOCl-Bi24O31Cl10核壳微球的合成及光催化

doi:10.11949/0438-1157.20220358

摘要/Abstract

摘要：

调整禁带宽度和抑制光生电子-空穴对复合是提高Bi₂O₃半导体光催化性能的重要途径。首先采用溶液合成和热处理法成功制备了SiO₂@Bi₂O₃核壳微球，研究了投料比、热处理温度等因素来调控核壳组成和包覆效果。为提高光催化活性，采用Cl掺杂改变SiO₂@Bi₂O₃核壳微球壳层的结构、形貌与组成，通过XRD、SEM、TEM等方法确定了微球壳层为BiOCl-Bi₂₄O₃₁Cl₁₀复合物。调整摩尔比、氨水和NaCl用量等参数，优化SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀核壳微球的均匀包覆效果，大幅提高了对罗丹明B（RhB）的光催化降解效率。在此基础上，阐述了SiO₂@Bi₂O₃核壳微球的形成机理和SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀核壳微球的光催化降解机理。

关键词: 太阳能, 催化剂, 纳米粒子, 复合材料, 二氧化硅

Abstract:

Tuning the band gap and suppressing the recombination of photogenerated electron-hole pairs are important ways to improve the photocatalytic performance of Bi₂O₃semiconductors. Firstly, SiO₂@Bi₂O₃ core-shell microspheres were successfully prepared by solution synthesis and heat treatment methods. And the core-shell composition and coating effect were controlled by the factors of changing feed ratio and heat treatment temperature. In order to further improve the photocatalytic activity, the structure, morphology and composition of SiO₂@Bi₂O₃ core-shell microspheres were changed by Cl doping. According to XRD, SEM and TEM, the shell structure of the microspheres was determined as BiOCl-Bi₂₄O₃₁Cl₁₀ complex. The uniform coating effect of SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀ core-shell microspheres was optimized by adjusting the molar ratio and dosages of ammonia and NaCl, where the photocatalytic degradation efficiency of rhodamine B was greatly improved. Based on the above results, the formation mechanism of SiO₂@Bi₂O₃ core-shell microspheres and the photocatalytic degradation mechanism of SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀ core-shell microspheres were reasonably proposed.

Key words: solar energy, catalyst, nanoparticles, composites, silica

中图分类号:

TQ 135.3

张鑫, 许蕊, 路馨语, 牛永安. SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀核壳微球的合成及光催化[J]. 化工学报, 2022, 73(8): 3636-3646.

Xin ZHANG, Rui XU, Xinyu LU, Yong'an NIU. Synthesis and photocatalysis of SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀ core-shell microspheres[J]. CIESC Journal, 2022, 73(8): 3636-3646.

图/表 13

表1 SiO2@Bi2O3样品前体的反应参数

Table 1 Reaction parameters of some SiO2@Bi2O3 sample precursors

样品	Bi(NO₃)₃·5H₂O/g	SiO₂/g	投料比x
SB-0.8	0.3032	0.0500	0.8
SB-1.0	0.4043	0.0500	1.0
SB-1.5	0.6065	0.0500	1.5
SB-2.0	0.8086	0.0500	2.0

表2 SiO2@BiOCl-Bi24O31Cl10样品前体的具体投料参数

Table 2 Specific feeding parameters of SiO2@BiOCl-Bi24O31Cl10 sample precursors

样品	氨水/ml	Bi(NO₃)₃∙5H₂O/g	NaCl/g	SiO₂∶Bi(NO₃)₃∙5H₂O∶NaCl(摩尔比)
SBC-1 (SBC-1-0.5)	0.5	0.4043	0.0488	1∶1∶1
SBC-2	0.5	0.4043	0.0975	1∶1∶2
SBC-3	0.5	0.4043	0.1462	1∶1∶3
SBC-4	0.5	0.4043	0.1950	1∶1∶4
SBC-1-1	1.0	0.4043	0.0488	1∶1∶1
SBC-1-2	2.0	0.4043	0.0488	1∶1∶1
SBC-1-3	3.0	0.4043	0.0488	1∶1∶1

图1 SB-1样品在空气条件的TG-DSC曲线

Fig.1 TG-DSC curves of sample SB-1 under air condition

图2 经过不同温度热处理后所得样品的XRD谱图

Fig.2 XRD patterns of as-obtained smaples after heat treatment at different temperatures

图3 SB-x经过400，450和500℃热处理后所得样品的SEM图

Fig.3 SEM images of as-obtained samples after the heat treatment of SB-x at 400, 450 and 500℃

图4 SiO2@Bi2O3核壳微球可能的形成机理

Fig.4 Possible formation mechanism of SiO2@Bi2O3 core-shell mircospheres

图5 SBC-y经450℃处理后所得产物的XRD谱图

Fig.5 XRD patterns of SBC-y after heat treatment at 450℃

图6 SBC-1、SBC-2样品及其450℃处理后所得产物的SEM图

Fig.6 SEM images of SBC-1 and SBC-2 samples and their products after 450℃ treatment

图7 SiO2@Bi2O3(450)-1.0和SiO2@BiOCl-Bi24O31Cl10(450)-1的TEM图

Fig.7 TEM images of SiO2@Bi2O3(450)-1.0 and SiO2@BiOCl-Bi24O31Cl10(450)-1 samples

图8 改变氨水添加量(z=0.5,1.0,2.0,3.0)和摩尔比(y=1,2,3,4)得到的SiO2@BiOCl-Bi24O31Cl10(450)的紫外可见吸收光谱图

Fig.8 UV absorption spectra of as-obtained SiO2@BiOCl-Bi24O31Cl10(450) with altered ammonia content (z=0.5,1.0,2.0,3.0) and mole ratio (y=1,2,3,4)

图9 Cl掺杂前后的SiO2@Bi2O3(450)-1.0产物的带隙图

Fig.9 Band gap diagram of the SiO2@Bi2O3(450)-1.0 sample before and after Cl incorporation

图10 不同热处理温度的SiO2@Bi2O3，不同投料摩尔比的SiO2@BiOCl-Bi24O31Cl10(450)-y和不同氨水添加量的SiO2@BiOCl-Bi24O31Cl10(450)-1-z对RhB的光催化降解曲线和表观速率常数

Fig.10 The photocatalytic degradation curves and apparent rate constants of RhB obtained by SiO2@Bi2O3 with different heat treatment temperatures, SiO2@BiOCl-Bi24O31Cl10(450)-y with different feed mole ratios and SiO2@BiOCl-Bi24O31Cl10(450)-1-z with different ammonia additions

图11 SiO2@BiOCl-Bi24O31Cl10核壳微球可能的光催化降解RhB机理

Fig.11 Possible photocatalytic degradation of RhB by SiO2@BiOCl-Bi24O31Cl10 core-shell microspheres

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SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀核壳微球的合成及光催化

Synthesis and photocatalysis of SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀ core-shell microspheres

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